CN101203431B - 轻重量拉伸吹制模制pet共聚物容器和用来制造它的预型件 - Google Patents

轻重量拉伸吹制模制pet共聚物容器和用来制造它的预型件 Download PDF

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Publication number
CN101203431B
CN101203431B CN2006800220490A CN200680022049A CN101203431B CN 101203431 B CN101203431 B CN 101203431B CN 2006800220490 A CN2006800220490 A CN 2006800220490A CN 200680022049 A CN200680022049 A CN 200680022049A CN 101203431 B CN101203431 B CN 101203431B
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China
Prior art keywords
preform
container
stretch blow
blow molded
hoop
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Expired - Fee Related
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CN2006800220490A
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CN101203431A (zh
Inventor
石昱
张龙飞
C·C·谢尔朗格
罗杰·伊恩·穆尔
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Coca Cola Co
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Coca Cola Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/14—Making preforms characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Geometry (AREA)
  • Manufacturing & Machinery (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)

Abstract

一种用来制造拉伸吹制模制容器的注射模制预型件，具有从12至16的整体拉伸比，其中整体拉伸比是环向拉伸比和轴向拉伸比的乘积，其中环向拉伸比是从5.6至6.5，并且其中预型件包括常规PET共聚物，该常规PET共聚物使用为在容器成品下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重预型件具有在100℃和6.2bar下测量的从650至800ml的自由吹制体积。本发明也涉及由所述预型件制成的拉伸吹制模制容器。

Description

轻重量拉伸吹制模制PET共聚物容器和用来制造它的预型件
技术领域
本发明涉及预型件设计和由其制成的预型件、以及制造这样的预型件。本发明也涉及拉伸吹制模制容器和制造它的方法。
背景技术
聚(对苯二甲酸乙二酯)树脂虽然它们可能并且常常的确包含少量的添加成分，但在工业中通常也称作“PET”。PET广泛地用来制造用于果汁、水、碳酸软饮料(“CSD”)等的容器。PET由于其机械和隔气性能的优良组合被用于这些目的。
这里提到的PET容器是拉伸吹制模制容器。如由本领域的技术人员认识到的那样，拉伸吹制模制PET容器通过首先由PET树脂制备注射模制预型件而制造。PET树脂注射到具有一定构造的预型件模具中。在容器制造商的现有技术方法中，预型件的构造由最终瓶子尺寸和用来制备容器的聚合物的性能决定。在预型件的制备之后，预型件被吹制模制以提供拉伸吹制模制容器。
PET容器必须符合相当刚性的技术规格，特别是当用来在温暖气候和/或夏季月份盛放和存储碳酸饮料时。在这样的条件下，容器常常经受由在高温下容器中的高压引起的热膨胀，在工业上通常称作“蠕变”。膨胀增大容器侧壁中PET分子之间的空隙，因而允许CO2比在通常条件下更快地穿过侧壁逸出。膨胀也增大容器的顶部空间，这允许碳酸物从饮料逃逸到顶部空间区域中。不管碳酸物如何从封闭在容器中的饮料中释放，但碳酸物的损失是不希望的，因为当这发生时饮料将感到“平淡”。蠕变增大容器中的内部空间，这又减小容器中饮料的高度。这种减小的高度可转化成容器未完全充满的客户感觉，并且像这样，转化成产品质量下降的感觉。
PET容器性能与侧壁强度也是有关的。在存储和运输时，填充的PET容器通常以几层填充的容器在彼此顶部上堆积。这在容器上引起显著的竖直应力，这表现为大部分倚靠侧壁。如果没有足够的侧壁强度或在PET容器中的顶部负载，则瓶子可能在存储时或在使用时压溃。
此外，客户对容器质量的感觉表现为当正握着容器时对它的感觉。当客户握住容器并且挤压容器时，容器侧壁将变形。如果侧壁挠曲太大，则容器感觉太软，并且客户把这与产品质量不良相联系，即使产品与在较坚固包装中包装的产品相比具有相同质量。
本领域的技术人员会认识到，为了降低成本希望减小在制备PET容器时使用的PET的量。较低重量PET容器导致较低材料成本、在制造过程期间的较小能量使用及较低运输成本。较轻重量容器也提供较少固体废料，并且对环境具有较小不利影响。然而，对于减小每个容器的PET量，也牺牲以上提到的所希望的性能，因而进行在源材料减少与性能之间的平衡难以实现。
减小PET容器重量的现有技术方法一般集中在制备容器使用的聚合物量的减少上。容器重量可减小到通过性能测试表现出不显著牺牲容器在使用时的性能的量，尽管对于其中不使用阻隔涂层的现有技术减轻重量的方法看到容器性能的某种退化。一般地，上述容器性能直接涉及制备容器使用的PET树脂量。在轻重量容器的现有技术方法中，使用的较低PET树脂量将导致较薄壁的成品容器，并因此将导致成品容器的较低阻隔和强度性能。因而，在使PET容器的性能最大而同时试图减小PET容器重量之间的矛盾仍然是一种担心，特别是在较温暖气候中。
在容器制造过程期间的能量消耗直接涉及预型件的厚度，因为在较厚预型件中，有加热和冷却的较大聚合物质量存在。因此，一种减小与PET容器的制备有关的能量成本的方法是通过减小预型件的厚度减轻预型件的重量。用于这样做的现有技术方法涉及对于预型件设计进行型芯变化或空腔变化。型芯变化通过挖空预型件内壁的一部分增大预型件的内径。空腔变化不影响内径，而是除去预型件外壁的一部分。然而，预型件的厚度部分地涉及制备预型件使用的聚合物的自然拉伸比。就是说，聚合物的自然拉伸比确定预型件的拉伸比，预型件的拉伸比是与预型件的厚度相关的预型件内径和在成品部分下面预型件的高度的函数。预型件设计成具有比聚合物的自然拉伸比有些高的预型件拉伸比，因而通过拉伸PET树脂超越其优化结晶和取向的应变硬化点以创建具有可接受机械性能的不模糊或大体不模糊容器而使PET树脂的性能最大化。增大预型件的内径降低预型件拉伸比，这通过不使PET树脂的拉伸最大而影响最终容器性能。因此，在现有技术中已经理解，具有典型地在约13至16范围中的自然拉伸比的PET树脂的使用具有在容器制造过程中减小能量成本的限制，因为不能有效地减小预型件的厚度。
一种现有技术方法-其已经用来改进容器质量，通过使用较薄壁预型件经过减小周期时间提高生产率、及减小制造中的能量消耗，是降低允许预型件的减小拉伸比的聚合物的拉伸比。已经进行通过PET树脂本身的改性降低聚合物的拉伸比的尝试。这通过增大PET树脂的分子量或固有粘度(IV)已经实现，因为较高IV的PET树脂导致具有较低自然拉伸比的聚合物。然而，当增大PET树脂的IV时，聚合物将具有较高熔化粘度。当较高熔化粘度存在时，为处理聚合物必须使用较高熔化温度。这导致较多能量的使用，并且也导致在处理期间聚合物退化的更大可能。较高熔化温度也要求在注射模制期间的较长周期时间。由降低聚合物的拉伸比的这种方法导致的这些不利性能因而在减小预型件壁厚时超越上述任何好处。
降低聚合物拉伸比也可通过长链支化的添加而完成。然而，像改性PET树脂IV那样，这种方法也增加PET的熔化粘度，并且引起高IV聚合物的相同问题。因而，这种方法是不希望的。
鉴于以上，希望开发一种在处理期间不导致较高能量消耗的预型件设计。更进一步，希望开发一种在成品拉伸吹制模制容器中提供良好机械性能，如低热膨胀、良好侧壁刚度及不模糊或大体不模糊容器的预型件设计。更进一步，希望在注射模制预型件期间并因此在容器制造过程期间减小能量消耗。本发明满足这些目标。
发明内容
在一个方面，本发明涉及用来制备具有与现有技术拉伸吹制模制容器的那些可比较的机械和热性能的轻重量拉伸吹制模制容器的预型件。而进一步，本发明涉及设计预型件以优化置于在使用中的成品容器上的应力的方法。
根据本发明的一个方面，提供一种由注射模制预型件制备的拉伸吹制模制容器，该注射模制预型件具有从12至16的所述拉伸吹制模制容器相对于注射模制预型件的整体拉伸比，其中整体拉伸比是环向拉伸比和轴向拉伸比的乘积，其中所述拉伸吹制模制容器相对于注射模制预型件的环向拉伸比是从5.6至6.5，并且其中注射模制预型件包括常规PET共聚物，其特征在于：该常规PET共聚物具有使用为在容器成品下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重参考预型件在100℃和90psi下测量的从650至800ml的自由吹制体积。
根据本发明的另一个方面，提供一种用来制造拉伸吹制模制容器的注射模制预型件，具有从12至16的所述拉伸吹制模制容器相对于注射模制预型件的整体拉伸比，其中整体拉伸比是环向拉伸比和轴向拉伸比的乘积，其中所述拉伸吹制模制容器相对于注射模制预型件的环向拉伸比是从5.6至6.5，并且其中注射模制预型件包括常规PET共聚物，其特征在于：该常规PET共聚物具有使用为在容器成品下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重参考预型件在100℃和90psi下测量的从650至800ml的自由吹制体积。
本发明提供一种具有一定环向比和轴向比极限的预型件设计，该预型件设计允许具有与由相同材料制成的标准重量拉伸吹制模制容器可比较或优于它们的热和机械性能的轻重量拉伸吹制模制容器的生产，其中这样的容器使用在现有技术中可得到的PET树脂。本发明也包括一种制造这样的预型件的方法、和拉伸吹制模制容器及制造它们的方法。
根据本发明，通过增大在环向方向上的拉伸，用常规容器级PET共聚物(下文“CG PET共聚物或常规PET”)可制成容器以具有较高机械强度。本发明人已经发现，通过增大环向拉伸比而没有轴向拉伸比的显著变化，可制成具有可比较强度或在某些实例中具有增大机械强度的较轻重量的预型件。在另一个方面，本发明人已经发现一种新颖的预型件设计，该新颖的预型件设计在其制备时与具有常规设计的预型件相比使用减小量的聚合物，可用来制备具有优良性能的常规PET拉伸吹制模制容器。
更具体地说，本发明包括一种用来制造拉伸吹制模制容器的注射模制预型件，具有从约12至约16的整体拉伸比，其中整体拉伸比是环向拉伸比和轴向拉伸比的乘积，其中环向拉伸比是从约5.6至约6.5，其中轴向拉伸比是从约2.4至约2.7，并且其中预型件包括CGPET共聚物，该CG PET共聚物具有使用为在容器成品部分下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重预型件在100℃和90psi下测量的从约650至约800ml的自由吹制体积。此外，本发明包括一种通过吹制模制这样一种预型件制成的容器。在优选实施例中，预型件包括敞开端瓶口形成部分、中间瓶体形成部分及封闭瓶底形成部分。
本发明的另外优点在随后的详细描述中将部分地叙述，并且部分描述将是显而易见的，或者可以通过本发明的实践了解。本发明的优点将借助于在附属权利要求书中具体指出的元件和组合而实现和获得。应理解，以上一般描述和如下详细描述都是本发明的示范和解释性方面，并且不限制所要求保护的本发明。
附图说明
图1是按照本发明优选实施例用常规容器级PET共聚物制成的注射模制预型件的剖视图。
图2是按照本发明优选实施例由图1的预型件制成的吹制模制容器的剖视图。
具体实施方式
通过参考本发明的如下详细描述和这里提供的例子及这里讨论的附图，可以更容易地理解本发明。应理解，本发明不限于描述的特定方法、构成及条件，因此当然可以变化。还应理解，这里使用的术语仅为了描述具体方面的目的，而不打算去限制。
在本说明书和在随后的权利要求书中，将提到物品的数量，它将定义成具有如下意思。
单数形式“一”、“一个”及“所述个”包括多个对象，除非另外清楚地规定。
范围在这里可以表达为从“约”一个具体值和/或至“约”另一个具体值。当表达这样一种范围时，另一个方面包括从一个具体值和/或至另一个具体值。类似地，当值通过先行字“约”的使用表达为近似时，要理解具体值形成另一个方面。
“选择性的”或“选择性地”意味着，以后描述事件或环境可能出现或可能不出现，并且描述包括其中所述事件或环境出现的情况、和其中它不出现的情况。例如，短语“选择性地包括一种成分”是指，组分可能包括该成分，并且描述既包括包含该成分的组分又包括没有该成分的组分。
本发明提供一种具有一定环向比和轴向比极限的预型件设计，该预型件设计允许具有与由相同材料制成的标准重量拉伸吹制模制容器可比较或优于它们的热和机械性能的轻重量拉伸吹制模制容器的生产，其中这样的容器使用在现有技术中可得到的PET树脂。本发明也包括一种制造这样的预型件的方法、和拉伸吹制模制容器及制造它们的方法。
根据本发明，通过增大在环向方向上的拉伸，用常规容器级PET共聚物可制成容器以具有较高机械强度。本发明人已经发现，通过增大环向拉伸比而没有轴向拉伸比的显著变化，可制成较轻重量具有可比较强度或在某些实例中具有增大机械强度的预型件。在另一个方面，本发明人已经发现一种新颖预型件设计，该新颖预型件设计在其制备时与具有常规设计的预型件相比使用减少量的聚合物，可用来制备具有优良性能的常规PET拉伸吹制模制容器。
在描述本发明时，容器级PET共聚物(下文“CG PET共聚物”)定义为具有使用为在容器成品部分下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重预型件在100℃和90psi下测量的从约650至约800毫升(ml)的自由吹制体积。这种CG PET共聚物这里也将称作常规PET。
CG PET共聚物与定义为具有使用为在容器成品下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重预型件在100℃和90psi(每平方英寸)下测量的从约400至约650(ml)的自由吹制体积的低自然拉伸比共聚物(下文“LNSR PET共聚物”)相反。标题为“用于低自然拉伸比PET共聚物的预型件、用其制造的容器及方法”并且提交于2005年5月11日的共同待审申请的公开通过参考特意包括在这里，公开了一种预型件，该预型件关于一定环向比和轴向比极限具有减小的拉伸比，相对于由在现有技术中可得到的PET树脂制成的预型件，由具有较低自然拉伸比的LNSR聚合物制成。这个参考文件也公开了一种具有优良机械性能的拉伸吹制模制容器，特别是饮料容器，由这种预型件设计制成。而且，这个参考文件公开了一种透明容器、或大体透明、不模糊或大体不模糊拉伸吹制模制容器。此外，LNSR聚合物独立地公开在于2004年10月18日提交在美国专利和商标局的共同待审美国专利申请No.10/967,803中，并且在其中要求保护，该专利申请是于2003年10月30日提交在美国专利和商标局的美国专利申请No.10/696,858的继续申请，后者按照35U.S.C.§119要求于2002年11月1日提交的美国临时专利申请序列号为60/423,221的优先权，该申请的公开也通过参考特意全部包括在这里。
自由吹制体积具有与聚合物的自然拉伸比的相关值，该值测量较困难并且要求使用专用仪器。净聚合物的自由吹制体积测量，如这里在例子中表示的那样，提供一种测量聚合物的自然拉伸比的方法。聚合物的自然拉伸比通过确定在吹制模制过程中由聚合物性能对预型件赋予的最小拉伸比极限而影响预型件设计。因而，自由吹制体积是这里选择的描述聚合物的自然拉伸比的方法。把为在容器成品部分下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的标准25克重预型件选作基础测量，并且使用100℃和90psi的标准试验条件，如在例1中表示的那样。对于具有在上述范围中的自由吹制体积的容器级PET共聚物，这样的共聚物的自然拉伸比是从约12至约16。对于具有在上述范围中的自由吹制体积的LNSR PET共聚物，这样的共聚物的自然拉伸比是从约8至约12。
预型件拉伸比是用来在这里描述本发明的另一个值。预型件拉伸比指的是在本领域中熟知的术语，并且根据如下公式定义：
(1)整体拉伸比＝[(最大容器内径/预型件内径)]×[(容器完成后的高度)/(预型件完成后的高度)]
(2)环向拉伸比＝(最大容器内径/预型件内径)
(3)轴向拉伸比＝(容器完成后的高度)/(预型件完成后的高度)
(4)或者，在可选择表示中，整体拉伸比＝环向拉伸比×轴向拉伸比
为了使具体聚合物的性能特征最大，预型件设计必须是这样的，从而预型件整体拉伸比大于PET共聚物的自然拉伸比。使用以上计算，将认识到，实际上有得到或设计供具体PET共聚物使用的规定预型件拉伸比的无限方式。然而，本发明人这里已经确定，尽管人们可修改轴向和环向拉伸比以提供规定的预型件整体拉伸比，但按照本发明，有一种必须遵循以在最终容器中实现最佳机械性能和阻隔性能的关系。
根据本发明的一个方面，本发明的用来使用CG PET共聚物制造拉伸吹制模制容器的注射模制预型件设计成具有从约12至约16，或从12至16的整体拉伸比。具体地说，在这些特定整体拉伸比内，环向拉伸比是从约5.6至约6.5，或从5.6至6.5，或从约5.7至约6.5。轴向拉伸比是从约2.4至约2.7，或从2.4至2.7。CG PET共聚物具有使用为在容器成品部分下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重预型件在100℃和90psi下测量的从约650至约800ml的自由吹制体积。在另一个方面，CG PET具有从约650至约750ml的自由吹制体积。
通过在这些范围内改变环向和轴向拉伸比以提供特定整体拉伸比公式，这里由本发明人已经发现，可提供具有改进性能，如较大热稳定性、重量较轻及较低能量消耗的拉伸吹制模制容器。这些性能改进对于在容器内包含的饮料产品具有多个好处，像例如饮料存放寿命的改善。借助于本发明也发现透明或大体透明预型件和拉伸吹制模制容器。
在拉伸吹制模制容器中，容器一般符合圆柱的形状。作为这种一般圆柱形状的结果，在使用期间，特别是在碳酸软饮料的使用期间，作用于结构上的应力在环向方向上与在轴向方向上不同。一般地说，在环向方向上的应力是在轴向方向上的应力的约两倍。对于碳酸软饮料，在容器侧壁上由内部压力引起的应力可使容器拉伸。这种现象对于本领域的技术人员也称作蠕变。蠕变对产品质量以及容器质量有害。具体地说，蠕变增大容器的体积，这又降低容器的表面填充液位。这对于客户可引起容器中有较少产品的错觉。蠕变可引起改变容器形状的容器变形，该容器形状在许多情况下代表品牌。蠕变也增大CSD的顶部空间体积。这使CO2从饮料跑到顶部空间，并因此减少在饮料中的CO2量。由于CSD的存放寿命由在饮料中的CO2量确定，所以增大的顶部空间体积明显地减小CSD产品的存放寿命。热量加剧这种现象，引起甚至更大的热膨胀或蠕变。
为CG PET共聚物设计的常规预型件典型地具有从约12至约16的整体拉伸比、在从4.3至5.5范围中的环向拉伸比及在从2.4至2.8范围中的轴向拉伸比。本发明人发现，有可能增大预型件的环向拉伸以在这个方向上实现较高取向，同时减小轴向拉伸以降低在这个方向上的取向。通过这样做，实现较高程度的环向取向。由于容器的取向涉及预型件拉伸比，所以较高环向拉伸可增大在环向方向上的取向，并因而减小在环向方向上的变形。由这种探索，已经发现，可能有益的是把预型件在环向方向上比在轴向方向上拉伸较大程度。在这样做时，已经发现，在环向方向上的较大拉伸改进生成饮料容器的取向，因而导致改进的容器性能。
由本发明的预型件设计制成的轻重量容器令人惊奇地呈现出等于或好于以较重重量由具有常规设计的预型件制成的饮料容器呈现的性能，如较高侧壁刚度。具体地说，本发明的拉伸吹制模制容器至少在重量上比由CG PET共聚物(即常规PET)和使用常规预型件设计制备的拉伸吹制模制容器轻。就是说，由本发明预型件设计制成的容器，与由具有约12至约16的整体拉伸比、从约2.4至约2.8的轴向拉伸比及从约4.3至约5.5的环向拉伸比的预型件(下文“常规设计”)制成的具有相同体积的第二容器相比，具有至少5％的重量减小。在另一个方面，预型件设计具有至少10％的重量减小。这样的发明轻重量容器呈现出等于或好于现有技术拉伸吹制模制容器的机械和热性能。此外，得到不模糊或大体不模糊容器。
已经发现，可改变预型件的物理尺寸，从而制成重量比在现有技术中制造具有类似物理性能的相同容器通常可能轻的预型件。尽管这种预型件重量较轻，但令人惊奇地发现，生成容器呈现出可接受水平的强度，并且与使用具有常规重量的预型件的常规设计由常规PET制成的容器相比，也提供可比较的容器侧壁刚度。本发明的这种设计不推荐用于常规重量预型件。本发明的这种设计为轻重量目的专门设计。否则，如果用于常规重量预型件，则侧壁厚度太厚，导致周期时间的不利结果。
使用这里讨论的本发明预型件设计方法，容器可用存在的减小量的聚合物生产，并且与现有技术减轻重量过程相比，仍然得到成品容器性能的可比较性能。这样的容器重量轻，但仍然呈现出改进的机械和热性能，具有增强的机械性能、较高结晶度，并且利用具有从约12至约16的拉伸比可实现改进的存放寿命。
本发明预型件设计与现有技术预型件设计技术不同，因为符合特定公式的预型件按非比例方式改变环向拉伸比和轴向拉伸比。这提供具有环向和轴向拉伸比的成品拉伸吹制模制容器，该环向和轴向拉伸比增强成品拉伸吹制模制容器的侧壁刚度。
转到图1，具有常规设计的预型件10在图1中示出。在图1中的尺寸没有按比例画出。
在本发明的一个方面通过注射模制CG PET共聚物制成预型件10。这样的预型件包括螺纹瓶颈成品部分12，该螺纹瓶颈成品部分12在盖顶凸缘14中在其下端部处终止。在盖顶凸缘14下面，有在逐渐减小外径的段18中终止的一般圆柱形段16，以便提供增大的壁厚。在段18下面，有细长瓶体段20。从盖顶凸缘14到细长瓶体段20的封闭端部21测量预型件的高度。
在图1中表明的预型件10被吹制模制以形成在图2中表明的容器22。容器22包括外壳24，该外壳24包括限定瓶口28的螺纹瓶颈成品部分26、在螺纹瓶颈成品部分下面的盖顶凸缘30、从盖顶凸缘延伸的锥形段32、在锥形段下面延伸的瓶体段34及在容器的底部处的瓶底36。从盖顶凸缘30到在瓶底36处的封闭端测量容器的高度。容器22适于用来制成包装饮料38，如在图2中表明的那样。包装饮料38包括在容器22中的如碳酸软饮料的饮料和密封容器的瓶口28的瓶盖40。
在本发明的一个方面，发明预型件的中间瓶体形成部分可具有从约1.5至约8mm的壁厚。预型件的中间瓶体形成部分也可具有从约10至约30mm的内径，并且预型件的高度-其从与成品部分相对的预型件的封闭端到成品部分延伸，是从50至150mm。在一个方面，按照本发明某些方面制成的容器可具有在从约0.25至约3升的范围内的体积和约0.25至约0.65mm的壁厚。然而，重要的是要注意，关于本发明的预型件设计，整体拉伸比和轴向和环向拉伸比必须按照这里叙述的公式变化。
在本说明书中，参考预型件10和生成容器22的尺寸。预型件的高度H是从与成品部分12相对的预型件的封闭端21到成品部分的盖顶凸缘14的距离。预型件10的内径ID是在预型件的细长瓶体段20的内壁之间的距离。预型件10的壁厚T也在预型件的细长瓶体段20处测量。容器22的高度H′是从与成品部分26相对的容器的瓶底36的封闭端到成品部分的盖顶凸缘30的距离。最大容器内径MD是沿容器22的高度在其最宽点处的容器直径。预型件的环向拉伸比等于最大容器内径除以预型件内径，并且轴向拉伸比等于在成品部分下面的容器高度除以在成品部分下面的预型件高度。预型件的整体拉伸比等于环向拉伸比和轴向拉伸比的乘积。
预型件10、容器22及包装饮料38只不过是本发明的典型实施例。应该理解，包括本发明一个方面的CG PET共聚物可用来制成具有各种构造的各种预型件和容器。
本发明人已经令人惊奇地确定，预型件设计的新颖方法可用来通过使用CG PET共聚物制备改进预型件设计，该CG PET共聚物是具有比在上文和在共同待审专利申请中描述的LNSR PET聚合物高的拉伸比的PET。本发明的预型件设计方法可用来由CG PET共聚物制备轻重量拉伸吹制模制容器。对于本发明预型件设计有用的CGPET共聚物的例子包括具有变体的PET共聚物，其为从约1至约5摩尔％、或从1至约3摩尔％的1，4-环己烷二甲醇变体，或可选择地，从约1至约5摩尔％、或从1至约3摩尔％的间苯二酸或萘二甲酸变体。在另一个方面，CG PET共聚物是指其中DEG是PET制造过程的天然副产品并且这种DEG在使用之前不被除去的PET。这样的DEG含量大于约2.4摩尔％DEG，或大于约3摩尔％DEG。如以前讨论的那样，DEG由本领域的技术人员认为是PET制造过程的无害副产品。像这样，通常用来制备饮料容器的PET必定包含DEG。直到这里描述的本发明，由这样的常规PET还不能制备可买到的可接受的轻重量拉伸吹制模制容器，因为由减少聚合物含量生成的薄壁不能提供成品容器的适当性能。
在本发明的另一个方面，提供一种用来制造容器的方法，其中该方法包括吹制模制注射模制预型件，该注射模制预型件如这里别处描述的那样具有用于CG PET共聚物的本发明的预型件设计的环向、轴向及整体拉伸比的关系。
为了理解本发明一个方面的意义，提供制造拉伸吹制模制容器的常规过程的概述。首先，由常规聚酯酯化/缩聚过程得到的PET丸粒被熔化，并且随后通过使用已知方法的注射模制过程形成预型件。第二，预型件在炉中加热到聚合物Tg以上的温度，并且然后经已知吹制模制过程形成容器。希望的最终结果是具有足够机械和阻隔性能的透明预型件和透明容器，以提供对于在容器内存储的包含饮料或食品的适当保护。
如由本领域的技术人员理解的那样，在生产透亮或透明容器时重要的考虑是，首先生产透亮或透明预型件。在注射模制步骤期间，热诱导结晶可出现在聚合物到预型件的转换期间。热诱导结晶往往在聚合物中导致巨大晶粒的形成，伴随有模糊的形成。为了使晶粒的形成最小化并因而提供透亮预型件，热结晶的速率应该足够慢，从而可生产具有很少或没有晶粒的预型件。然而，如果热结晶的速率太慢，则可能不利地影响PET树脂的生产速率，因为PET必须在固态聚合之前热晶化，固态聚合是一种用来增大PET的分子量并且同时除去有害乙醛的过程。固态聚合增大聚合物的分子量，从而由聚合物制成的容器将具有必需的强度。
用来减少热结晶速率的现有技术工艺包括使用包含一定量的共聚用单体的PET。最普遍使用的共聚用单体调节剂是间苯二酸或1，4-环己烷二甲醇，它们在从1.5至3.0摩尔％的范围内的水平下被添加。
均衡减小在注射模制期间的热结晶速率的需要是，增大在吹制模制期间发生的应变诱导结晶度的速率的需要。应变诱导结晶度由PET的快速机械变形生成，并且产生极小的、透明的晶粒。在容器侧壁中存在的晶粒的量与容器的强度和阻隔性能相关。
具体地说，预型件设计的现有技术方法一直基于型芯变化或空腔变化、或在常规预型件设计中具有类似环向和轴向拉伸比的预型件的重新设计。这些现有技术设计没有考虑在成品容器中在环向和轴向方向上施加的不同应力。本发明人在这里已经确定，由于在成品容器中施加的不同应力，需要比轴向拉伸大的环向拉伸。
由于提供有本设计的当在规定整体拉伸比内变化时在轴向拉伸比与环向拉伸比之间的平衡，容易拉伸预型件。在使环向取向最大的同时，生成拉伸吹制模制容器的热和机械性能。
另外，对于CG PET共聚物使用本发明的预型件，已经发现可制成具有相同或类似侧壁刚度和热膨胀特性的轻重量容器。如较高重量的现有技术常规容器那样。
用于使用发明预型件设计的轻重量潜力容器可用两个试验表明：如在这里下面呈现的例子中所描述的热膨胀和侧壁挠曲。两个试验都证明容器的机械性能。分别地，热膨胀是热膨胀的反映，并且侧壁挠曲是侧壁刚度的反映。与预型件设计无关，对于相同树脂组分，较轻重量瓶子一般呈现较低机械强度、较差热稳定性(及伴随较大热膨胀)、及较小侧壁刚度(或较大侧壁挠曲)。热稳定性和侧壁刚度的改进性能可实质上减小蠕变，这是在通过直径和高度变化测得的在容器应力下的尺寸变化。这在使用中是重要因素，特别是对于碳酸软饮料，因为在填充过程期间和之后大多数容器经受某种应力，特别是机械应力和来自加热的应力。而且，在存储和运输期间的过高温度也可把机械应力置于容器上。因此，热膨胀和侧壁挠曲试验在这里用来比较容器的性能，并且特别是加压容器的性能。
本发明的预型件设计可用来制造拉伸吹制模制容器。这样的容器包括但不限于，瓶子、鼓形物、玻璃水瓶及冷却器等。如本领域的技术人员熟知的那样，通过吹制模制注射模制预型件可制成这样的容器。适当预型件和容器结构及用来制造它们的方法的例子公开在美国专利No.5,888,598中，该专利的公开也通过参考全部包括在这里。按照本发明也可制备对于本领域技术人员知道的其它预型件和拉伸吹制模制容器。
以上描述了本发明，并且下面通过例子进一步表明，例子绝不应解释成对本发明的范围施加限制。相反，要清楚地理解，可以采用各种其它实施例、修改及其等效物，这些在阅读这里的描述之后将呈现在本领域的技术人员眼前，而不脱离本发明的精神和/或附属权利要求书的范围。
例子
如下例子被提出从而为本领域的技术人员提供用于使用常规PET的PET瓶子的轻重量的本发明的预型件设计的完整公开和描述，并且打算是本发明的纯粹示范而不打算限制本发明人作为其发明的范围。已经进行努力以保证相对于数值(例如，量、温度等等)的精度，但应该涉及某些误差和偏差。除非另有说明，份是按重量的份，温度是℉或在室温下，并且压力是在大气压下或接近大气压。
例1
不同PET树脂在真空炉中在135℃下过夜干燥，以在注射模制之前实现低于50ppm的湿度水平。用试验室规模的Arburg(阿博格)单元空腔注射机进入常规预型件模具中使用为在容器成品部分下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重预型件进行注射模制。然后预型件自由吹制到汽泡以确定每种聚合物的拉伸比。对于每种预型件变型进行自由吹制，并且气泡在100℃的温度和90psi下吹制。自由吹制体积是PET的自然拉伸比的指示，并且针对每个气泡进行记录。自由吹制体积越大，PET的自然拉伸比越高。
表1：LNSR PET共聚物和CG PET共聚物的自由吹制结果
Figure GSB00000270291900161
具有3摩尔％IPA和2.8摩尔％的DEG的第一树脂是CG PET共聚物或常规PET共聚物。由表1看到，其它树脂具有减小的自由吹制体积，并因而呈现比常规PET共聚物低的自然拉伸比。
例2
为600ml PET瓶设计26.5g预型件和23g预型件。两种预型件设计的拉伸比表示在表2中。通过来自生产600ml瓶子使用的28g预型件的型芯变化得到26.5g预型件。
表2
例3
适于用来制备具有0.84的IV的CSD容器的可买到级PET在真空炉中在135℃下过夜干燥，以在注射模制之前实现低于50ppm的湿度水平。根据本公开这种树脂认为是“常规的”，因为这种树脂不被处理以除去从制造过程导出的残余DEG。用试验室规模的Arburg单元空腔注射机进入26.5g和23g预型件模具中进行注射模制。预型件然后用Sidel SBO 1机器吹制模制成600ml轮廓瓶。
例4
对于来自例3的瓶子按如下进行热稳定性测量：
测量“所接收的”试验瓶子尺寸和厚度。然后瓶子用碳酸水填充到4.1+/-0.1的体积，并且盖上瓶盖。填充瓶子暴露于环境温度过夜，并且测量尺寸以确定百分数变化。瓶子暴露于38℃下，并且测量尺寸以确定百分数变化。
关键尺寸变化列在表3中。
表3：用常规PET制成的瓶子的热稳定性
Figure GSB00000270291900171
以上结果表明，通过的23-g瓶子在稳定性测试期间具有较少尺寸变化。具体地说，26.5-g瓶子比23-g瓶子重得多(即，较厚的壁)，并因此期望在热稳定性试验中表现得好得多。令人惊奇地，使用本发明预型件设计制备的较轻PET容器，比这种较重容器表现出显著好的热稳定性。这种结果表明，本发明的预型件设计方法可用来制备具有令人惊奇良好的热稳定性的轻重量拉伸吹制模制容器。
例5-环境应力龟裂阻力
例4的瓶子经受下面所描述的加速应力龟裂试验。为了加速应力龟裂阻力测试，随机选择每个变量的二十五(25)个试样，并且充碳酸气到4.1-4.5体积的CO2。把试样在72℉和50％RH下存储24小时。然后把这些瓶子每一个的瓶底区域浸入在稀释氢氧化钠(0.1％)溶液中。然后在3小时的过程中认真检查每个瓶子，以便探测穿过瓶底裂纹的二氧化碳泄漏或摧毁性瓶底失效。如果探测到任何碳酸泄漏或瓶底破坏，则记录到这个失效点的时间。
表4：加速应力龟裂
Figure GSB00000270291900181
如从表4看到的那样，即使26.5g瓶子重得多23g瓶子也表现得超过26.5g瓶子，并且期望在苛性钠应力龟裂试验中持续得较长。这个试验结果表明，使用本发明的预型件设计方法由常规PET制备的拉伸吹制模制容器呈现优于由现有技术预型件设计制备的容器的机械性能。这种结果是令人惊奇的，因为希望较厚的26.5g容器表现得更好。这种结果进一步证实对于本发明的预型件设计方法看到的优良结果。
对于本领域的技术人员显而易见的，在本发明中可进行各种修改和变更，而不脱离本发明的范围。本发明的其它方面对于本领域的技术人员来说考虑到说明书和这里公开的本发明的实践将是显而易见的。意欲使说明书和例子仅当作示范。

Claims (9)

1.一种由注射模制预型件制备的拉伸吹制模制容器，该注射模制预型件具有从12至16的所述拉伸吹制模制容器相对于注射模制预型件的整体拉伸比，其中整体拉伸比是环向拉伸比和轴向拉伸比的乘积，其中所述拉伸吹制模制容器相对于注射模制预型件的环向拉伸比是从5.6至6.5，并且其中注射模制预型件包括常规PET共聚物，其特征在于：该常规PET共聚物具有使用为在容器成品下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重参考预型件在100℃和90psi下测量的从650至800ml的自由吹制体积。
2.根据权利要求1所述的拉伸吹制模制容器，其中，注射模制预型件的环向拉伸比是从5.7至6.5。
3.根据权利要求1所述的拉伸吹制模制容器，其中，常规PET共聚物的自由吹制体积是从650至750ml。
4.根据权利要求1所述的拉伸吹制模制容器，包括从23至25g的常规PET共聚物，其中，容器的体积是从450至650ml。
5.根据权利要求1所述的拉伸吹制模制容器，与由具有12至16的整体拉伸比及从4.3至5.5的环向拉伸比的第二预型件制成的第二容器相比，所述拉伸吹制模制容器具有至少5％的重量减小，其中所述第二容器包括与所述拉伸吹制模制容器一样的常规PET共聚物且与拉伸吹制模制容器具有相同体积。
6.根据权利要求5所述的拉伸吹制模制容器，具有至少10％的重量减小。
7.一种用来制造拉伸吹制模制容器的注射模制预型件，具有从12至16的所述拉伸吹制模制容器相对于注射模制预型件的整体拉伸比，其中整体拉伸比是环向拉伸比和轴向拉伸比的乘积，其中所述拉伸吹制模制容器相对于注射模制预型件的环向拉伸比是从5.6至6.5，并且其中注射模制预型件包括常规PET共聚物，其特征在于：该常规PET共聚物具有使用为在容器成品下具有65mm最大直径和200mm高度的500ml容器设计的、并且具有5.5的环向拉伸比和2.6的轴向拉伸比的25克重参考预型件在100℃和90psi下测量的从650至800ml的自由吹制体积。
8.根据权利要求7所述的注射模制预型件，其中，注射模制预型件的环向拉伸比是从5.7至6.5。
9.根据权利要求7所述的注射模制预型件，其中，常规PET共聚物的自由吹制体积是从650至750ml。
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JP2008540185A (ja) 2008-11-20
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JP5175717B2 (ja) 2013-04-03
BRPI0609387B1 (pt) 2018-11-21
RU2390482C2 (ru) 2010-05-27
WO2006124199A1 (en) 2006-11-23
BRPI0609387B8 (pt) 2020-05-26
ATE485222T1 (de) 2010-11-15
CA2607504C (en) 2014-03-11
RU2007145082A (ru) 2009-06-20
US20100098894A1 (en) 2010-04-22
ES2354718T3 (es) 2011-03-17
AU2006248005A1 (en) 2006-11-23
CA2607504A1 (en) 2006-11-23
AR054116A1 (es) 2007-06-06
AU2006248005B2 (en) 2011-04-28
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EP1885602B9 (en) 2011-03-30
ZA200709637B (en) 2008-11-26
US7820257B2 (en) 2010-10-26
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US20060257603A1 (en) 2006-11-16
US8247049B2 (en) 2012-08-21

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